Bisazo compounds and use thereof as fiber reactive dyes

ABSTRACT

A bisazo compound of the following formula: ##STR1## wherein R 1  and R 3  are each hydrogen or alkyl; D is phenylene or naphthylene; one of X 1  and X 2  is NH 2  and the other is OH; Z 1  and Z 2  are each --CH═CH 2  or --CH═CH 2  Z&#39; in which Z&#39; is a splittable group; B is monosulfophenylene, monosulfophenylene-methylene or mono- or di-sulfonaphthylene-methylene; U is phenylene or an aliphatic bridging group; and J is an amono-derivative group or, J may be alkoxy when X 1  is OH and U is phenylene, and J may be alkoxy or phenoxy when X 1  is OH and U is the aliphatic bridging group. This compound is useful for dyeing or printing fiber materials and gives a dyed or printed product having a color superior in various fastness properties with superior build-up property.

This is a division of application Ser. No. 08/188,755, filed Jan. 31,1994, now U.S. Pat. No. 5,478,927.

The present invention relates to improved compounds useful for dyeing orprinting hydroxy group-and/or amide group-containing materials such ascellulose fiber, natural or synthetic polyamide fiber, polyurethanefiber, leather and mixed fibers thereof to give navy blue-colored dyedproducts superior in light fastness, perspiration-light fastness and wetfastness, and to application of said compounds.

Bisazo compounds having a triazinyl group and a plurality ofvinylsulfone type reactive groups in the molecule are disclosed in U.S.Pat. No. 5,053,494 and U.S. Pat. No. 5,112,959. However, they are stillinsufficient in the dye performance and await for improvementparticularly with respect to dyeing power, build-up property andfastness properties.

A variety of reactive dyes have widely been used for dyeing and printingfiber materials. The actual level of technology, however, is not yetsatisfactory for meeting high demands with respect to applicability tospecific dyeing technology and fastness properties of dyed or printedproducts.

The known reactive dyes mentioned above are insufficient in dyeperformance such as dyeing power or build-up property and in fastnessproperties such as light fastness, perspiration-sunlight fastness andwet fastness, so that the development of a further improved dye isintensely desired.

Excellence in build-up property is very important today when therequirement for an economical dyeing method has reached a high level,and excellence in fastness properties is also very important today whena high level of quality has become required in the field of clothes,etc.

The present inventors have undertaken extensive studies to improve theabove-mentioned known dyes to find a novel compound satisfying the needsfor dyes. As a result, the present invention has been accomplished.

The present invention provides a bisazo compound represented by thefollowing formula (I) or a salt thereof: ##STR2## wherein R¹ is hydrogenor unsubstituted or substituted alkyl;

D is phenylene unsubstituted or substituted with one or two substituentsselected from sulfo, alkoxy, alkyl, halogeno and carboxy, or naphthyleneunsubstituted or substituted once or twice by sulfo;

one of X¹ and X² is NH₂ and the other is OH;

Z¹ is --CH═CH₂ or --CH₂ CH₂ Z' in which Z' is a group capable of beingsplit by the action of an alkali;

B is a group represented by the following formula (1) or (2): ##STR3##wherein the mark * means a bond linking to an azo group, and R² ishydrogen, methyl or methoxy; and

when X¹ is OH, L is a triazinyl group represented by any one of thefollowing formulas (II) to (V): ##STR4## wherein R³ is hydrogen orunsubstituted or substituted alkyl;

R⁴ is hydrogen, alkyl, alkoxy or halogeno;

R⁵ and R⁶ independently of one another are each hydrogen orunsubstituted alkyl, or R⁵ and R⁶ conjointly form a heterocyclic ringwhich may contain nitrogen, oxygen or sulfur as a ring atom;

R⁷ is straight or branched alkyl unsubstituted or substituted with oneor two substituents selected from alkoxy, sulfo, carboxy, carboxylicester, hydroxy, cyano, sulfato, halogeno, carbamoyl and sulfamoyl;

R⁸ is straight or branched alkyl unsubstituted or substituted with oneor two substituents selected from alkoxy, sulfo, carboxy, carboxylicester, hydroxy, cyano, sulfato, halogeno, phenyl, substituted phenyl,carbamoyl and sulfamoyl, or phenyl unsubstituted or substituted with oneor two substituents selected from alkyl, substituted alkyl, alkoxy,substituted alkoxy, hydroxy, sulfo, cyano, carboxy, carboxylic ester,sulfamoyl, carbamoyl, substituted amino and halogeno;

R¹⁰ is hydrogen or straight or branched alkyl unsubstituted orsubstituted with one or two substituents selected from hydroxy,halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic ester,carbamoyl, sulfamoyl, amino and substituted amino;

R¹¹ is hydrogen, straight or branched alkyl unsubstituted or substitutedwith one or two substituents selected from hydroxy, halogeno, alkoxy,cyano, sulfo, sulfato, carboxy, carboxylic ester, carbamoyl, sulfamoyl,amino and substituted amino, or phenyl unsubstituted or substituted withone or two substituents selected from sulfo, alkyl, substituted alkyl,alkoxy, substituted alkoxy, hydroxy, halogeno, cyano, carboxy,carboxylic ester, carbamoyl, sulfamoyl, amino, substituted amino, --SO₂CH₂ CH₂ OH and SO₂ Z³, in which Z³ is --CH═CH₂ or --CH₂ CH₂ Z' in whichZ' is as defined above; or

R¹⁰ and R¹¹ conjointly form a heterocyclic ring which may containnitrogen, oxygen or sulfur as a ring atom;

Z² is --CH═CH₂ or --CH₂ CH₂ Z' in which Z' is as defined above; and

A is a divalent aliphatic group represented by the following formula(3), (4) or (5):

    --CH.sub.2 --W--,                                          (3)

    --(CH.sub.2).sub.m --O--(CH.sub.2).sub.n --,               (4) ##STR5## in which W is straight or branched chain C.sub.1 -C.sub.6 alkylene unsubstituted or substituted by chloro, bromo, fluoro, hydroxy, sulfato, cyano, C.sub.1 -C.sub.4 alkylcarbonyloxy, C.sub.1 -C.sub.5 alkoxycarbonyl, carboxy or carbamoyl; W.sup.1 and W.sup.2 independently of one another are each straight or branched chain C.sub.2 -C.sub.6 alkylene; R.sup.9 is hydrogen, unsubstituted lower alkyl or phenyl; and m and n independently of one another are each an integer of 2 to 6; and

when X¹ is NH₂, L is a triazinyl group represented by the formula (III)or (V) described above.

The present invention also provides a method for dyeing or printingfiber materials by using a bisazo compound of the formula (I) or a saltthereof.

In the formula (I), examples of R¹ are hydrogen, straight or branchedchain C₁ -C₆ alkyl unsubstituted, straight or branched chain C₁ -C₆alkyl substituted by hydroxy, halogeno, cyano, carboxy or sulfo, and thelike. Of these, preferred R¹ is hydrogen or straight or branched chainC₁ -C₄ alkyl unsubstituted, and especially preferred is hydrogen ormethyl.

The groups preferred as D include, for example, unsubstituted phenylene,phenylene substituted with one or two substituents selected from C₁ -C₄alkyl such as methyl or ethyl, C₁ -C₄ alkoxy such as methoxy or ethoxy,halogeno such as chloro or bromo, sulfo and carboxy, unsubstitutednaphthylene, and naphthylene substituted once or twice by sulfo.Specific examples of D are as follows: ##STR6## wherein the mark ***means a bond linking to an azo group. Of these, particularly preferredare those having a sulfo group in the ortho position relative to the azogroup. Examples of particularly preferred D include the following:##STR7## wherein the mark *** is as defined above.

The group capable of being split by the action of an alkali representedby Z' include, for example, sulfuric acid ester group, thiosulfuric acidester group, phosphoric acid ester group, acetic acid ester group andhalogen. Of these, sulfuric acid ester group and halogen are preferred.Preferred Z¹, Z² and Z³ are each independently vinyl, β-sulfatoethyl orβ-chloroethyl.

Examples of the group B include the following: ##STR8## wherein themark * is as defined above. Of these, preferred are: ##STR9## whereinthe mark * is as defined above, and the like.

In the formulas (II), (III), (IV) and (V), examples of R³ include thesame groups as R¹. Of these, preferred are hydrogen and unsubstituted,straight or branched chain C₁ -C₄ alkyl, and particularly preferred arehydrogen, methyl and ethyl.

In the formulas (II) and (III), examples of R⁴ include hydrogen, loweralkyl, lower alkoxy, chloro, bromo and fluoro. Of these, preferred arehydrogen, methyl and methoxy.

In the formula (III), R⁵ and R⁶ can be hydrogen or unsubstituted,straight or branched chain C₁ -C₄ alkyl. Of these, preferred arehydrogen, methyl and ethyl.

In the formula (III), when R⁵ and R⁶ conjointly form a heterocyclicring, the group --NR⁵ R⁶ may be a heterocyclic residue which is usually5- or 6-membered one. Examples of said heterocyclic residue includethose containing only one nitrogen atom as a hetero atom, thosecontaining a nitrogen atom and one or two hetero atoms selected fromnitrogen, oxygen and sulfur, and the like. Specific examples of theheterocyclic residue include the residues derived from pyrrolidine,piperidine, piperazine, N-alkylpiperazine, morpholine, pyrrole,imidazole and the like. Of these, preferred is a residue derived frommorpholine, namely morpholino.

In the combination of R⁵ and R⁶, preferred are a case where --NR⁵ R⁶ ismorpholino and cases where at least one of R⁵ and R⁶ is hydrogen and theother is hydrogen, methyl or ethyl.

In the formula (III), the compounds represented by H--NR⁵ R⁶ which canbe used for forming the residue --NR⁵ R⁶ are, for example, ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, dimethylamine, diethylamine,methylethylamine, pyrrolidine, piperazine, morpholine, piperidine,pyrrole, imidazole and the like. Of these, particularly preferred areammonia, methylamine, ethylamine and morpholine.

In the formula (II), R⁷ is straight or branched chain alkylunsubstituted or substituted by alkoxy, sulfo, carboxy, carboxylicester, hydroxy, cyano, sulfato, halogeno, carbamoyl or sulfamoyl.Examples of the alkyl include methyl, ethyl, propyol, isopropyl, butyl,isobutyl, sec-butyl, 2-hydroxyethyl, 2-sulfatoethyl, 2-sulfoethyl,2-methoxyethyl, 2-chloroethyl, 2-carboxyethyl and the like. Of these,preferred are unsubstituted C₁ -C₄ alkyl such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl and the like, and particularlypreferred are methyl and ethyl.

In the formula (II), the compounds represented by R⁷ OH which can beused for forming a group --OR⁷ substituting the triazine ring include,for example, methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol,2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol,2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid,2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acidand the like.

Of these, preferred --OR⁷ are the residues derived from methanol,ethanol, n-propanol and isopropanol, namely methoxy, ethoxy, n-propoxyand isopropoxy, and particularly preferred are methoxy and ethoxy.

In the formulas (IV) and (V), A is a divalent aliphatic grouprepresented by any one of the above formulas (3), (4) and (5). Any ofthe free bonds in these groups may link to --SO₂ Z².

In the formula (5), R⁹ can be hydrogen, C₁ -C₄ alkyl or phenyl. Ofthese, preferred are hydrogen, methyl and ethyl.

Particularly preferred as A are the residues of the following formulas(6), (7) and (8):

    --CH.sub.2 CH.sub.2 --,                                    (6)

    --CH.sub.2 CH.sub.2 CH.sub.2 --,                           (7)

    --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --.                 (8)

In the formula (IV), as the unsubstituted or substituted alkylrepresented by R⁸, straight or branched chain C₁ -C₄ lower alkyl groupsare preferred. As the substituent which may be present in said alkyl,preferred are C₁ -C₄ alkoxy, sulfo, carboxy, carboxylic ester, hydroxy,cyano, sulfato, halogeno, phenyl, sulfophenyl, carbamoyl and sulfamoyl.When a plurality of substituents are present, they may be identical ordifferent from one another preferred R⁸ are, for example, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, benzyl, 2-hydroxyethyl,2-sulfatoethyl, 2-sulfoethyl, 2-methoxyethyl, 2-chloroethyl,2-carboxyethyl and the like. Of these, particularly preferred areunsubstituted C₁ -C₄ alkyl such as methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl and the like, and most preferred are methyland ethyl. The unsubstituted or substituted phenyl represented by R⁸ ispreferably phenyl unsubstituted or substituted by one or twosubstituents selected from the group consisting of, for example, C₁ -C₄alkyl, C₁ -C₄ alkoxy, hydroxy, sulfo, carboxy, sulfamoyl, carbamoyl,chloro and bromo. Of these, particularly preferred are phenyl, 2-, 3- or4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-, 3- or 4-chlorophenyl, 2-,3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl and the like. Among thealkyl and phenyl groups mentioned above, the unsubstituted orsubstituted phenyl groups are more preferable as R⁸.

The compounds represented by R⁸ OH which can be used for forming a group--OR⁸ substituting the triazine ring in the formula (IV) include, forexample, the following:

aromatic compounds such as phenol, 1-hydroxy-2-, -3- or-4-methylbenzene, 1-hydroxy-3,4- or -3,5-dimethylbenzene, 1-hydroxy-2-,-3- or -4-ethylbenzene, 1-hydroxy-2-, -3- or -4-methoxybenzene,1-hydroxy-2-, 3- or -4-ethoxybenzene, 1-hydroxy-2-, -3- or-4-chlorobenzene, 3- or 4-hydroxyphenylmethanesulfonic acid,3-hydroxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid,5-hydroxybenzene-1,3-disulfonic acid, 6-hydroxybenzene-1,4-disulfonicacid, 4-hydroxybenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid,5-hydroxybenzene-1,3-dicarboxylic acid,5-hydroxy-2-ethoxybenzenesulfonic acid and the like, and

aliphatic compounds such as methanol, ethanol, n-propanol, isopropanol,n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol,2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol,2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid,2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionicacid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4-methylbenzylalcohol, 2-, 3- or 4-sulfobenzyl alcohol, 2-phenylethanol,1-phenyl-2-propanol and the like.

Of these, preferred are groups --OR⁸ derived from phenols unsubstitutedor substituted by methyl, methoxy or sulfo or from methanol, ethanol,n-propanol and isopropanol, namely phenoxy, 2-, 3- or 4-methylphenoxy,2-, 3- or 4-methoxyphenoxy, 2-, 3-or 4-sulfophenoxy, methoxy, ethoxy,n-propoxy and isopropoxy, and particularly preferred are phenoxy,methylphenoxy, methoxyphenoxy and sulfophenoxy.

In the formula (V), R¹⁰ is hydrogen or straight or branched chain alkylunsubstituted or substituted by hydroxy, halogeno, alkoxy, cyano, sulfo,sulfato, carboxy, carboxylic ester, carbamoyl, sulfamoyl, amino orsubstituted amino. Preferred examples of such alkyl are methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxyethyl,3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-chloroethyl,2-bromoethyl, 2-sulfoethyl, 2-carboxyethyl, 2-carbamoylethyl,2-sulfatoethyl, 2-sulfamoylethyl and the like. Of these, preferred aremethyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl and 2-carboxyethyl.

In the formula (V), R¹¹ is hydrogen, alkyl unsubstituted or substitutedby one or two substituents selected from hydroxy, halogeno, alkoxy,cyano, sulfo, sulfato, carboxy, carboxylic ester, carbamoyl, sulfamoyl,amino and substituted amino such as dimethylamino, or phenylunsubstituted or substituted by one or two substituents selected fromsulfo, alkyl, alkoxy (said alkyl and alkoxy may be further substituted),hydroxy, halogeno, cyano, carboxy, carboxylic ester, sulfamoyl,carbamoyl, amino, substituted amino such as dimethylamino, --SO₂ CH₂ CH₂OH and --SO₂ Z³, wherein Z³ is the same as the above-defined Z¹. As suchalkyl, the alkyl groups enumerated as examples for R¹⁰ are applicable.Of these, preferred are methyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl and2-carboxyethyl. As such phenyl, preferred are phenyl, 2-, 3- or4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2-,3- or 4-bromophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or4-hydroxyphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-,3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl,2-methoxy-5-methylphenyl, 2,5-dimethoxyphenyl, 2,5-dimethylphenyl,##STR10## and the like.

As the group represented by --NR¹⁰ R¹¹, preferred are the same groups asexemplified for H--NR⁵ R⁶ as well as the groups derived from thefollowing amines represented by H--NR¹⁰ R¹¹ :

aniline, N-methylaniline, N-ethylaniline, o-, m- or p-toluidine, o-, m-or p-anisidine, 2-, 3- or 4-anilinesulfonic acid, 2,4- or2,5-anilinedisulfonic acid, 2-, 3- or 4-chloroaniline, 2-, 3- or4-bromoaniline, 2-, 3- or 4-fluoroaniline, 2-, 3- or 4-anilinecarboxylicacid, N-methyltoluidine (o-, m- or p-isomer), N-ethyltoluidine (o-, m-or p-isomer), N-methylchloroaniline (2-, 3- or 4-isomer),N-ethylchloro-aniline (2-, 3- or 4-isomer), aminophenol (o-, m- orp-isomer), and ##STR11##

Of these, preferred groups --NR¹⁰ R¹¹ are those derived from ammonia,methylamine, ethylamine, 2-hydroxyethylamine, 2-sulfoethylamine,2-carboxyethylamine, aniline, N-methylaniline, N-ethylaniline, 2-, 3- or4-anilinesulfonic acid, ##STR12##

When R¹⁰ and R¹¹ conjointly form a ring, the ring may be the same one asexemplified for --NR⁵ R⁶.

Among the amines represented by H--NR¹⁰ R¹¹ for forming the group --NR¹⁰R¹¹ and exemplified above, the aromatic amines (i.e. aniline and itsderivatives) are particularly preferred.

The compounds of the invention exist in the form of a free acid or asalt thereof. Of the salts, preferred are alkali metal salts andalkaline earth metal salts, and particularly preferred are sodium salt,potassium salt and lithium salt.

The compounds of the invention can be produced, for example, in thefollowing manner. Thus, a compound of the formula (I) can be produced bysubjecting 2,4,6-trihalogeno-s-triazine of the formula (XII): ##STR13##wherein T is halogen, to a successive condensation with a bisazocompound represented by the following formula (VI) in the free acidform: ##STR14## wherein B, D, R¹, X¹, X² and Z¹ are as defined above, acompound selected from the compounds of the formulas (VIIa) and (VIIb):##STR15## wherein R³, R⁴, A and Z² are as defined above, and a compoundselected from the compounds of the formulas (VIII) to (XI):

    H--OR.sup.7 (VIII), H--OR.sup.8,                           (IX)

    H--NR.sup.5 R.sup.6 (X), H--NR.sup.10 R.sup.11,            (XI)

wherein R⁵, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are as defined above, in anarbitrary order.

As the 2,4,6-trihalogeno-s-triazine, preferred are cyanuric chloride andcyanuric fluoride.

Preferable orders of condensation with 2,4,6-trihalogeno-s-triazine areas follows. Thus, when a compound of the formula (I) in which L is agroup of the formula (II) or (IV) is synthesized from a compound of theformula (VIII) or (IX), it is preferable to carry out the condensationof the compound of the formula (VIII) or (IX) primarily or secondarily,and particularly preferably primarily. When a compound of the formula(I) in which L is a group of the formula (III) is synthesized from acompound of the formula (X), it is preferable to carry out thecondensation of the compound of the formula (X) primarily orsecondarily.

When a compound of the formula (I) in which L is a group of the formula(II) or (III) is synthesized from a compound of the formula (VIIa), thecondensation of the compound of the formula (VIIa) can be carried outprimarily, secondarily or tertiarily with excellent results, and it ispreferably carried out secondarily or tertiarily.

When a compound of the formula (I) in which L is a group of the formula(IV) is synthesized from a compound of the formula (VIIb), it ispreferable to carry out the condensation of the compound of the formula(VIIb) primarily or secondarily.

When a compound of the formula (I) in which L is a group of the formula(V) is synthesized from a compound of the formula (VIIb), it ispreferable to carry out the condensation of the compound of the formula(VIIb) primarily or secondarily, and particularly primarily.

When a compound of the formula (I) in which L is a group of the formula(V) is synthesized from a compound of the formula (XI), it is preferableto carry out the condensation of the compound of the formula (XI)primarily or secondarily in case that R¹¹ is an aliphatic group, andsecondarily or tertiarily in case that R¹¹ is an aromatic group.

In all the case mentioned above, however, the order of condensationreactions is not limited and the reaction conditions are also notlimited. Generally speaking, the primarily reaction is carried out at atemperature of from -10° C. to +40° C. at a pH value of from 1 to 10,the secondary reaction is carried out at a temperature of from 0° C. to70° C. at a pH value of from 2 to 10, and the tertiary reaction iscarried out at a temperature of from 10° C. to 100° C. at a pH value offrom 2 to 9, by which a compound of the formula (I) or a salt thereofcan be obtained.

Alternatively, the compounds of the invention can be synthesized in thefollowing manner, too. Thus, by using a diamine compound of thefollowing formula (XIII): ##STR16## wherein B and R¹ are as definedabove, as a component of condensation in place of the bisazointermediate compound of the formula (VI) used in the production processmentioned above, the same synthesis procedure as above is carried out toobtain an amine compound of the following formula (XIV): ##STR17##wherein B, R¹ and L are as defined above. Apart from it, an aminecompound of the following formula (XV):

    Z.sup.1 --SO.sub.2 --D--NH.sub.2,                          (XV)

wherein Z¹ and D are as defined above, is prepared. Both the aminecompounds are separately diazotized in a usual manner and coupled with acompound represented by the following formula (XVI) in the free acidform: ##STR18## in an arbitrary order, whereby a compound of the formula(I) can be obtained. The coupling reaction can be made to progressprimarily at a temperature of from -10° C. to +30° C. at a pH value offrom 0 to 4, and secondarily at a temperature of from 0° C. to 40° C. ata pH value of from 2 to 8.

As the compound of the formula (XVI), preferred are H acid representedby the formula (9) and K acid represented by the formula (10): ##STR19##Of these, further preferred is H acid of the formula (9).

As a third alternative, a compound of the formula (I) can be synthesizedalso by coupling a compound of the above-mentioned formula (XVI) in anarbitrary order with diazo components constituted of an amine compoundof the above-mentioned formula (XV) and one of the following compounds(XVII) to (XXIII) as diazo components: ##STR20## wherein T, R¹, B, R⁵,R⁶, R³, R⁴, Z², A, R⁷, R⁸, R¹⁰ and R¹¹ are as defined above, followed bysecondary and/or tertiary condensation reaction. In this method, if adiazo compound selected from the compounds of the formulas (XVII) to(XXIII) is primarily coupled with a compound of the formula (XVI), thesecondary and/or tertiary condensation reaction may be carried out at astage of monoazo intermediate compound before preparing the bisazocompound.

When the groups represented by Z¹ and Z² are each --CH₂ CH₂ Z' whereinZ', namely a group capable of being split by the action of an alkali, isan ester group such as sulfuric acid ester group, phosphoric acid estergroup or the like, the ester group may be formed after the condensationor the coupling reaction. That is to say, a compound of the formula (I)can be obtained by carrying out the same reaction procedure as above byusing the following compounds (XXIV), (XXV), (XXVI) and (XXVII) in placeof the compounds of (VIIa), (VIIb), (VI) and (XV), respectively, used inthe above-mentioned production: ##STR21## wherein R³, R⁴, A, X¹, X², B,R¹ and D are as defined above, and, at an arbitrary stage, esterifyingthe precursor of ester compound thus obtained in the conventional mannerand treating the product in the same manner as above.

Examples of the chromophore usable in the invention, namely the compoundof the formula (VI) in which SO₂ Z¹ is hydrogen, include the following:

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(5"-amino-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(5"-amino-2"-sulfophenylazo)-8-aminonaphthalene-3,5-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,5-disulfonicacid,

1-hydroxy-2-(1',7'-disulfonaphth-2'-ylazo)-7-(5"-amino-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(1",7"-disulfophenylnaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonic acid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(6"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(8"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(6"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,5-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(4"-amino-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfo-5'-aminomethylnaphth-2'-ylazo)-7-(2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(2'-sulfophenylazo)-7-(1"-sulfo-5"-aminomethylnaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfo-5'-aminomethylnaphth-2'-ylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(1"-sulfo-5"-aminomethylnaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1',7'-disulfo-5'-aminomethyl-naphth-2'-ylazo)-7-(2"-sulfophenylazo)-8-amino-naphthalene-3,6-disulfonicacid,

1-hydroxy-2-(2'-sulfophenylazo)-7-(1",7"-disulfo-5"-aminomethylnaphth-2"-ylazo)-8-amino-naphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-aminomethyl-4'-methyl-2'-sulfophenylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(5"-aminomethyl-4"-methyl-2"-sulfophenylazo)-8-amino-naphthalene-3,6-disulfonicacid,

1-hydroxy-2-(2'-sulfophenylazo)-7-(5"-amino-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-(2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(1",7"-disulfo-5"-aminomethylnaphth-2"-ylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(5"-amino-4"-methyl-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-7-phenylazo-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1-sulfonaphth-2'-ylazo)-7-(4"-amino-5"-methoxy-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(1-sulfonaphth-2'-ylazo)-7-(5"-amino-4"-methoxy-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(2'-sulfophenylazo)-7-(4"-amino-5"-methoxy-2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid,

1-hydroxy-2-(4'-amino-5'-methoxy-2'-sulfophenylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-amino-naphthalene-3,6-disulfonic acid,

1-hydroxy-2-(5'-amino-4'-methoxy-2'-sulfophenylazo)-7-(1"-sulfonaphth-2"-ylazo)-8-amino-naphthalene-3,6-disulfonicacid and

1-hydroxy-2-(4'-amino-5'-methoxy-2'-sulfophenylazo)-7-(2"-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonicacid.

Of the compounds represented by the formula (I) according to the presentinvention, preferred are those represented by the following formulas (E)and (F) each in the free acid form: ##STR22## wherein Z¹ and L are asdefined above, R¹² is hydrogen or sulfo, and R²² and R²³ independentlyof one another are each hydrogen, methyl, methoxy or sulfo.

Preferred compounds of the formula (E) include, for example, thoserepresented by the following formulas (E-1) to (E-4) each in the freeacid form: ##STR23## wherein Z¹ and R¹² are as defined above, R¹⁴ ismethyl or ethyl, and Q is a group represented by the following formula(K-1) or (K-2): ##STR24## in which R¹³ is hydrogen, methyl or ethyl, andZ² is as defined above; ##STR25## wherein Z¹, Z², R¹² and R¹³ are asdefined above, R¹⁵ is hydrogen and R¹⁶ is hydrogen, methyl or ethyl orNR¹⁵ R¹⁶ is morpholino; ##STR26## wherein Z¹, Z² and R¹² are as definedabove, R¹⁷ is hydrogen and R¹⁸ is hydrogen, methyl, ethyl,2-hydroxyethyl, phenyl, sulfophenyl, methylphenyl, methoxyphenyl,hydroxyphenyl or carboxyphenyl, or NR¹⁷ R¹⁸ is morpholino. R¹⁸ isparticularly preferably unsubstituted or substituted phenyl mentionedabove; ##STR27## wherein Z¹, Z² and R¹² are as defined above, and R²⁴and R²⁵ independently of one another are each hydrogen, sulfo, methyl,ethyl, methoxy, ethoxy, chloro or carboxy.

Other preferred compounds encompassed within the formula (E) are, forexample, represented by the following formulas (E-5) to (E-12) each inthe free acid form: ##STR28## wherein R¹³ and R¹⁴ are as defined above;##STR29## wherein R¹⁴ is as defined above, and G is a divalent aliphaticgroup represented by the earlier mentioned formula (6), (7) or (8);##STR30## wherein R¹³, R¹⁵ and R¹⁶ are as defined above; ##STR31##wherein G, R¹⁷ and R¹⁸ are as defined above; ##STR32## wherein R¹³ andR¹⁴ are as defined above; ##STR33## wherein R¹³, R¹⁵ and R¹⁶ are asdefined above; ##STR34## wherein G, R²⁴ and R²⁵ are as defined above;and ##STR35## wherein G, R²⁴ and R²⁵ are as defined above.

Preferred compounds of the formula (F) include, for example, thoserepresented by the following formula (F-1)in the free acid form:##STR36## wherein Z¹, Z², R²² and R²³ are as defined above, R¹⁹ ishydrogen, methyl or ethyl, and R²⁰ is hydrogen, methyl, ethyl,2-hydroxyethyl, phenyl, methylphenyl, methoxyphenyl, sulfophenyl,carboxyphenyl, chlorophenyl, hydroxyphenyl or 3- or4-(β-sulfatoethylsulfonyl)phenyl, or NR¹⁹ R²⁰ is morpholino.

Other preferred compounds encompassed within the formula (F) are, forexample, represented by the following formula (F-2) in the free acidform: ##STR37## wherein G and R¹⁹ are as defined above, and R²¹ isphenyl, methylphenyl, methoxyphenyl, chlorophenyl, sulfophenyl,carboxyphenyl or 3- or 4-(β-sulfatoethylsulfonyl)phenyl.

The compound of the present invention is fiber-reactive and useful fordyeing or printing hydroxyl group-containing and amide group-containingmaterials in a fibrous form including unmixed or mixed fibers.

The hydroxyl group-containing materials include natural or synthetichydroxyl group-containing materials such as cellulose fiber materials,regenerated products thereof and polyvinyl alcohol. Examples of thecellulose fiber materials are cotton and other vegetable fibers such aslinen, hemp, jute and ramie fibers. Examples of the regeneratedcellulose fibers are viscose staple and filament viscose.

The amide group-containing materials include synthetic or naturalpolyamide and polyurethane. Examples of the materials, particularly inthe fibrous forms, are wool and other animal furs, silk, leather,polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyeing may be carried out in a suitable manner, which can beselected from conventional manners depending on the physical andchemical properties of said fiber materials.

For example, cellulose fiber materials can be dyed using the compound byan exhaustion dyeing, padding including cold batch-up dyeing or printingmethod.

The exhaustion dyeing can be carried out at a relatively low temperaturein the presence of an acid binding agent such as sodium carbonate,trisodium phosphate, sodium hydroxide and the like, if desired, using aneutral salt such as sodium sulfate, sodium chloride and the like,together with a hydrotropic agent, a penetrant or a level dyeing agent.The neutral salt suitable for promoting the exhaustion may be added to adye bath before or after temperature reaching a desired level for thedyeing, if desired, dividedly.

The padding can be carried out by padding the fiber materials at ambienttemperature or an elevated temperature, and after drying, steaming ordry-heating the materials to perform the dye-fixation.

The printing can be carried out in a one-phase or two-phase manner. Theone-phase printing may be conducted by printing the fiber materials witha printing paste containing an acid binding agent such as sodiumhydrogencarbonate and the like, followed by steaming at a temperature of95° to 160° C. The two-phase printing may be conducted by printing thefiber materials with a neutral or weakly acidic printing paste, andpassing the materials through a hot alkaline bath containing anelectrolyte or over-padding the materials with an alkaline paddingliquor containing an electrolyte, followed by a steaming or dry-heatingtreatment.

For the preparation of the printing paste, a thickener or emulsifiersuch as sodium alginate, starch ether and the like may be used, ifdesired, together with a conventional auxiliary agent such as ureaand/or dispersing agent.

The acid binding agent useful for fixing the compound of the presentinvention on the cellulose fiber materials includes water-soluble basicsalts consisting of alkali or alkaline earth metals and inorganic ororganic acids or compounds capable of liberating alkali under heatingconditions. Preferred are alkali metal hydroxides and alkali metal saltsof inorganic or organic acids having a weak or medium strength.Particularly preferred are sodium salts and potassium salts. Examplesthereof are sodium hydroxide, potassium hydroxide, sodiumhydrogencarbonate, sodium carbonate, sodium formate, potassiumcarbonate, sodium dihydrogenphosphate, disodium hydrogenphosphate,trisodium phosphate, sodium silicate, sodium trichloroacetate and thelike.

The dyeing of natural or synthetic polyamide and polyurethane fibermaterials can be carried out by performing exhaustion in an acid or weakacid bath, while controlling the pH value, and then making the bathneutral, or in some cases alkaline to perform the fixation. The dyeingtemperature ranges usually from 60° to 120° C. In order to achieve alevel dyeing, there may be used a conventional level dyeing agent suchas condensation product between cyanuric chloride and 3 times by mole ofaminobenzenesulfonic acid or aminonaphthalene-sulfonic acid, or anaddition product between stearylamine and ethylene oxide, and the like.

The compound of the invention is characterized by excellent dyeperformance in the dyeing and printing of fiber materials, particularlycellulose fiber materials. For example, the compound can give a dyedproduct excellent in light fastness, perspiration-light fastness, wetfastness such as washing resistance, peroxide-washing resistance,chlorine resistance, perspiration resistance and acid-hydrolysisresistance, and alkali resistance, abrasion fastness and iron fastness.

Further, the compound of the invention can exhibit excellent dyeingpower, build-up property and washing off property, and high solubilityas well as exhaustion and fixation percentages. Moreover, the compoundof the invention can hardly be affected by dyeing temperature,quantities of dyeing assistants such as salt and alkali, and bathratios, and therefore can give dyed products of constant quality.

Furthermore, the dyed products obtained according to the invention arehard to be changed in color on a fix-treatment or resin-finishing, or incontact with a basic material during storage.

The compound of the invention can give good results also when used inthe form of a compounded mixture with any of the fiber-reactive dyesmentioned in, for example, JP-A-61-155469 (=EP-A-184071),JP-A-59-161463, JP-A-56-15481 (=EP-A-21105), JP-A-57-89679(=EP-A-52985), JP-A-60-6754, JP-A-50-178, JP-A-56-118976 (=EP-A-35171),JP-A-63-77974 (=EP-239847), JP-A-57-2365 (=EP-A-42108), JP-A-59-15451(=EP-A-99721), JP-A-56-9483 (=EP-A-22265), JP-A-60-123559 andJP-A-56-128380. Further, the compound of the invention can give goodresults when used in the form of a compounded mixture with any of thedyes marketed under the commercial names of Sumifix Supra, Sumifix,Levafix, Remazol and the like.

The present invention is illustrated in more detail with reference tothe following examples, which are only illustrative but not limitativeto the scope of the invention. In the examples, parts are by weight.

EXAMPLE 1

In a usual manner, 2,4-diaminobenzenesulfonic acid (3.76 parts) andcyanuric chloride (3.69 parts) were subjected to a condensation reactionwith each other at a pH value of 2-4 at a temperature of 0°-15° C.,followed by a condensation reaction with2-(β-hydroxyethylsulfonyl)ethylamine (3.06 parts) at pH 6-9 at atemperature of 15°-40° C. The resulting condensate was diazotized in ausual manner and the diazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH1-3.5 at a temperature of 0°-15° C., and further a diazotized product of2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts)was coupled therewith at pH 4-8 at a temperature of 0°-30° C. Then, thethus obtained product was condensed with 3-aminobenzenesulfonic acid(3.47 parts) at pH 2-5 at a temperature of 50°-80° C. The product thusobtained was converted to a sulfuric ester in a usual manner and saltedout to obtain a bisazo compound represented by the following formula inthe free acid form: ##STR38##

Example 2

The synthesis of Example 1 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 3-aminobenzenesulfonic acid and2-(β-hydroxyethylsulfonyl)ethylamine were replaced with the compoundsshown in column 2, column 3, column 4, column 5 and column 6 of thefollowing table, respectively, to obtain the corresponding bisazocompounds. When used for dyeing, the bisazo compounds gave dyed productsof which hues were as shown in column 7 of the table. Similar resultswere obtained when the above-mentioned synthesis was repeated whilechanging the order of primary and secondary condensation reactions withcyanuric chloride. Further, similar results were obtained also when thecyanuric chloride was replaced with cyanuric fluoride. Further, similarresults were obtained also when the compound of column 6 was replacedwith the corresponding sulfuric ester derivative and the final step,namely conversion to a sulfuric ester, was omitted.

    TABLE 1      - 1 2 3 4 5 6 7      1     ##STR39##      ##STR40##      ##STR41##      ##STR42##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      2 " "     ##STR43##      ##STR44##      " Navyblue      3     ##STR45##      "      ##STR46##      ##STR47##      " Navyblue      4 "     ##STR48##      "      ##STR49##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      5 "     ##STR50##      "      ##STR51##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      6     ##STR52##      ##STR53##      ##STR54##      ##STR55##      H.sub.2 NC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      7     ##STR56##      "      ##STR57##      ##STR58##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      8     ##STR59##      "      ##STR60##      ##STR61##      H.sub.2 NC.sub.4 H.sub.8 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      9     ##STR62##      "      ##STR63##      ##STR64##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.2 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     10      ##STR65##      ##STR66##      ##STR67##      ##STR68##      ##STR69##      Navyblue     11 " "      ##STR70##      ##STR71##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       12 " "      ##STR72##      ##STR73##      H.sub.2 NC.sub.3 H.sub.6 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     13      ##STR74##      "      ##STR75##      ##STR76##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       14      ##STR77##      ##STR78##      ##STR79##      ##STR80##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       15 " " "      ##STR81##      " Navyblue     16 " " "      ##STR82##      " Navyblue     17      ##STR83##      " "      ##STR84##      H.sub.2 C.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                      18 " " "      ##STR85##      " Navyblue     19      ##STR86##      ##STR87##      ##STR88##      ##STR89##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       20 " " "      ##STR90##      " Navyblue     21 " "      ##STR91##      ##STR92##      " Navyblue     22 " " "      ##STR93##      " Navyblue     23 " " "      ##STR94##      " Navyblue     24 " " "      ##STR95##      " Navyblue     25      ##STR96##      ##STR97##      ##STR98##      ##STR99##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       26 " " "      ##STR100##      " Navyblue     27 " " "      ##STR101##      " Navyblue     28 " " "      ##STR102##      " Navyblue     29 " " "      ##STR103##      " Navyblue     30      ##STR104##      " "      ##STR105##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       31      ##STR106##      ##STR107##      ##STR108##      ##STR109##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       32 " " "      ##STR110##      " Navyblue     33 " " "      ##STR111##      " Navyblue     34 " " "      ##STR112##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     35 " " "      ##STR113##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     36 " " "      ##STR114##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     37 " " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue     38      ##STR115##      ##STR116##      ##STR117##      ##STR118##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       39      ##STR119##      " "      ##STR120##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       40 " "      ##STR121##      ##STR122##      " Navyblue     41 " "      ##STR123##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      42 " "      ##STR124##      " H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      43      ##STR125##      ##STR126##      ##STR127##      ##STR128##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       44      ##STR129##      "      ##STR130##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      45 "      ##STR131##      ##STR132##      ##STR133##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       46      ##STR134##      ##STR135##      ##STR136##      ##STR137##      " Navyblue     47      ##STR138##      "      ##STR139##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      48      ##STR140##      ##STR141##      ##STR142##      ##STR143##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       49 " "      ##STR144##      ##STR145##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       50      ##STR146##      "      ##STR147##      ##STR148##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       51      ##STR149##      ##STR150##      ##STR151##      ##STR152##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       52      ##STR153##      ##STR154##      ##STR155##      ##STR156##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue

Example 3

In a usual manner, 2-aminobenzenesulfonic acid (3.47 parts) and cyanuricchloride (3.69 parts) were subjected to a condensation reaction witheach other at pH 2-5 at a temperature of 0°-15° C., and then with2-(β-hydroxyethylsulfonyl)ethylamine (3.06 parts) at pH 6-9 at atemperature of 15°-40° C., and further with 2,4-diaminobenzenesulfonicacid (3.76 parts) at pH 2-5 at a temperature of 50°-80° C. The resultingcondensate was diazotized in a usual manner, and the diazotized productwas coupled with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39parts) at pH 1-3.5 at a temperature of 0°-15° C., and then a diazotizedproduct of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid(8.23 parts) was coupled therewith at pH 4-8 at a temperature of 0°-30°C. The product of coupling reaction thus obtained was converted to asulfuric ester in a usual manner and salted out to obtain a bisazocompound represented by the following formula in the free acid form:##STR157##

Example 4

The same procedure as in Example 3 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 2-aminobenzenesulfonic acid and2-(β-hydroxyethylsulfonyl)ethylamine used in Example 3 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary and secondarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove. When the compound of column 6 (and/or the compound(s) of column 5and column 2 in case of having --SO₂ C₂ H₄ OH) was replaced with thecorresponding sulfuric ester derivative and the final step, namelyconversion to a sulfuric ester, was omitted, the results were similar tothose obtained above.

    TABLE 2      - 1 2 3 4 5 6 7      1     ##STR158##      ##STR159##      ##STR160##      ##STR161##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      2     ##STR162##      " "      ##STR163##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      3 " "     ##STR164##      ##STR165##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      4     ##STR166##      "      ##STR167##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                       5      ##STR168##      ##STR169##      ##STR170##      NH.sub.3 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue     6 " " " H.sub.2      NCH.sub.3 " Navyblue                     7 " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.3 H " Navyblue     8      ##STR171##      " " H.sub.2 NC.sub.2 H.sub.4 CO.sub.2 H H.sub.2 NC.sub.3 H.sub.6     SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      9     ##STR172##      " " H.sub.2 NC.sub.2 H.sub.4 OH H.sub.2 NC.sub.2 H.sub.4 SO.sub.2     C.sub.2 H.sub.4      OH Navyblue                    10      ##STR173##      ##STR174##      ##STR175##      ##STR176##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     11 "      ##STR177##      ##STR178##      HN(CH.sub.3).sub.2      ##STR179##      Navyblue     12      ##STR180##      ##STR181##      ##STR182##      H.sub.2      NCH.sub.3     ##STR183##      Navyblue     13      ##STR184##      "      ##STR185##      H.sub.2 NC.sub.2 H.sub.4 OH H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2     H.sub.4      OH Navyblue           14      ##STR186##      " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                          15      ##STR187##      ##STR188##      ##STR189##      ##STR190##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       16 " " "      ##STR191##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       17 " " " H.sub.2     NC.sub.2      H.sub.5 " Navyblue            18 " " "      ##STR192##      " Navyblue     19 " " "      ##STR193##      " Navyblue     20      ##STR194##      ##STR195##      ##STR196##      ##STR197##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     21 " " " NH.sub.3 H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2     C.sub.2 H.sub.4      OH Navyblue                    22 " " " H.sub.2 NC.sub.2 H.sub.4 OH H.sub.2 NC.sub.3     H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                     23 " " " H.sub.2 NC.sub.2 H.sub.4 Cl     H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                      24 " " " HN(CH.sub.3).su     b.2 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                       25      ##STR198##      " " NH.sub.3 " Navyblue     26 " " " H.sub.2 NC.sub.2      H.sub.5 " Navyblue                              27      ##STR199##      ##STR200##      ##STR201##      H.sub.2 NCH(CH.sub.3).sub.2 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4      OH Navyblue           28 " " "      ##STR202##      " Navyblue     29 " " "      ##STR203##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       30 " " " H.sub.2     NC.sub.2 H.sub.4 CO.sub.2 H H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4     SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             31 " " " H.sub.2 NC.sub.2 H.sub.5 H.sub.2     NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue     32 " " "      ##STR204##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     33      ##STR205##      ##STR206##      ##STR207##      ##STR208##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     34 " " "      ##STR209##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     35      ##STR210##      " "      ##STR211##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       36 " " "      ##STR212##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       37      ##STR213##      ##STR214##      ##STR215##      ##STR216##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       38 "      ##STR217##      ##STR218##      ##STR219##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       39 "      ##STR220##      ##STR221##      ##STR222##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       40      ##STR223##      "      ##STR224##      ##STR225##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       41      ##STR226##      ##STR227##      ##STR228##      ##STR229##      H.sub.2 NC.sub.2 H.sub.4 N(CH.sub.3)C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 N     avyblue     42 " " " " H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue     43      ##STR230##      " "      ##STR231##      " Navyblue     44      ##STR232##      "      ##STR233##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      45      ##STR234##      ##STR235##      ##STR236##      ##STR237##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue     46 "      ##STR238##      " " H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                        47      ##STR239##      ##STR240##      "      ##STR241##      " Navyblue     48 " " "      ##STR242##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     49      ##STR243##      ##STR244##      ##STR245##      ##STR246##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       50 " "      ##STR247##      ##STR248##      " Navyblue     51      ##STR249##      " "      ##STR250##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       52      ##STR251##      "      ##STR252##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      53      ##STR253##      ##STR254##      ##STR255##      ##STR256##      H.sub.2 NCH.sub.2 CH(CN)CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OH Navyblue     54 "      ##STR257##      "      ##STR258##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue

Example 5

In a usual manner, 2,4-diaminobenzenesulfonic acid (3.76 parts) andcyanuric chloride (3.69 parts) were subjected to a condensation reactionwith each other at pH 2-4 at a temperature of 0°-15° C., and then with3-(β-chloroethylsulfonyl)propylamine (3.72 parts) at pH 6-9 at atemperature of 15°-40° C., and further with 4-aminobenzenesulfonic acid(3.47 parts) at pH 2-5 at a temperature of 50°-80° C. The resultingcondensate was diazotized in a usual manner, and the diazotized productwas coupled with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39parts) at pH 1-3.5 at a temperature of 0°-15° C., and then a diazotizedproduct of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid(8.23 parts) was coupled therewith at pH 4-8 at a temperature of 0°-30°C. The product of coupling reaction thus obtained was salted out toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR259##

Example 6

The same procedure as in Example 5 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 4-aminobenzenesulfonic acid and3-(β-chloroethylsulfonyl)propylamine used in Example 5 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary, secondary and tertiarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove.

    TABLE 3      - 1 2 3 4 5 6 7      1     ##STR260##      ##STR261##      ##STR262##      H.sub.2 NC.sub.2 H.sub.4 CONH.sub.2 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 Navyblue      2 " " " H.sub.2 NC.sub.2 H.sub.5 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 Navyblue      3     ##STR263##      "      ##STR264##      NH.sub.3 H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2     Navyblue      4 "     ##STR265##      ##STR266##      ##STR267##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Navyblue      5 "     ##STR268##      ##STR269##      ##STR270##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue      6     ##STR271##      ##STR272##      ##STR273##      NH.sub.2 CH.sub.3 H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 Navyblue      7 " " "     ##STR274##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue     8 " " "      ##STR275##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue     9 " " "      ##STR276##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue     10 " " "      ##STR277##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                                                       11      ##STR278##      ##STR279##      ##STR280##      ##STR281##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                                                       12 " " "      ##STR282##      " Navyblue     13      ##STR283##      " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Navyblue                                             14 " " "      ##STR284##      " Navyblue     15 " " "      ##STR285##      " Navyblue     16      ##STR286##      ##STR287##      ##STR288##      ##STR289##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                                                       17 " " "      ##STR290##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue     18 " " " NH.sub.3 H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 Navyblue     19 " " " H.sub.2 NC.sub.4      H.sub.9 " Navyblue                              20 " " "      ##STR291##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2      CHCH.sub.2 Navyblue

Example 7

The same procedure as in Example 1 was repeated, except that thecoupling reactions of 1-amino-8-hydroxynaphthalene-3, 6-disulfonic acidwith the two diazo compounds were carried out in a reverse order, toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR292##

Example 8

The same procedure as in Example 7 was repeated, using the samecompounds of columns 2-6 as used in Example 2, to obtain thecorresponding bisazo compounds. When used for dyeing, the compounds gavenavy blue-colored dyed products. Similar results were obtained when theabove-mentioned synthesis was repeated while changing the order ofprimary and secondary condensation reactions with cyanuric chloride.Further, similar results were obtained also when cyanuric chloride wasreplaced with cyanuric fluoride. Further, similar results were obtainedalso when the compound of column 6 was replaced with the correspondingsulfuric ester derivative and the final step, namely conversion to asulfuric ester, was omitted.

Example 9

The same procedure as in Example 7 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 3-aminobenzenesulfonic acid and2-(β-hydroxyethylsulfonyl)ethylamine used in Example 7 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary and secondarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove. Further, similar results were obtained also when the compound ofcolumn 6 (and the compound of column 2 in case of having --SO₂ C₂ H₄ OH)was replaced with the corresponding sulfuric ester derivative and thefinal step, namely conversion to a sulfuric ester, was omitted.

    TABLE 4      - 1 2 3 4 5 6 7      1     ##STR293##      ##STR294##      ##STR295##      ##STR296##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      2 " " "     ##STR297##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      3     ##STR298##      " "      ##STR299##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      4 "     ##STR300##      "      ##STR301##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      5     ##STR302##      " " " H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue      6     ##STR303##      ##STR304##      ##STR305##      ##STR306##      H.sub.2 NC.sub.4 H.sub.8 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      7     ##STR307##      ##STR308##      "      ##STR309##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      8     ##STR310##      "      ##STR311##      ##STR312##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      9     ##STR313##      ##STR314##      ##STR315##      ##STR316##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             10 " " "      ##STR317##      " Navyblue      11 " " "      ##STR318##      " Navyblue      12 " " "      ##STR319##      " Navyblue      13 " " "      ##STR320##      " Navyblue      14 " " "      ##STR321##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             15      ##STR322##      ##STR323##      ##STR324##      ##STR325##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             16 " " "      ##STR326##      " Navyblue      17 " " "      ##STR327##      " Navyblue      18 " " "      ##STR328##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             19 " " "      ##STR329##      " Navyblue      20 " " "      ##STR330##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             21 " " "      ##STR331##      " Navyblue      22      ##STR332##      ##STR333##      ##STR334##      ##STR335##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      23 " " "      ##STR336##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             24 " " "      ##STR337##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             25 " " "      ##STR338##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             26 " " "      ##STR339##      " Navyblue      27 " " "      ##STR340##      " Navyblue      28      ##STR341##      ##STR342##      ##STR343##      ##STR344##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             29 " " "      ##STR345##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             30 " " "      ##STR346##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             31 " " "      ##STR347##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      32 " " "      ##STR348##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             33 " " "      ##STR349##      " Navyblue      34      ##STR350##      ##STR351##      ##STR352##      ##STR353##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             35 " " "      ##STR354##      " Navyblue      36 " " "      ##STR355##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             37 " " "      ##STR356##      " Navyblue      38 " " "      ##STR357##      " Navyblue      39 " " "      ##STR358##      " Navyblue      40      ##STR359##      ##STR360##      ##STR361##      ##STR362##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             41 " " "      ##STR363##      " Navyblue      42 " "      ##STR364##      ##STR365##      " Navyblue      43 " "      ##STR366##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue             44      ##STR367##      ##STR368##      ##STR369##      ##STR370##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                             45      ##STR371##      ##STR372##      ##STR373##      " " Navyblue      46      ##STR374##      "      ##STR375##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue             47      ##STR376##      "      ##STR377##      " H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH N     avyblue      48      ##STR378##      ##STR379##      ##STR380##      ##STR381##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue

EXAMPLE 10

The same procedure as in Example 3 was repeated, except that thecoupling reactions of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidwith the two diazo compounds were carried out in a reverse order, toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR382##

EXAMPLE 11

The same procedure as in Example 10 was repeated, using the samecompounds of columns 2-6 as used in Example 4, to obtain thecorresponding bisazo compounds. When used for dyeing, the compounds gavenavy blue-colored dyed products. Similar results were obtained when theabove-mentioned synthesis was repeated while changing the order ofprimary and secondary condensation reactions with cyanuric chloride.Further, similar results were obtained also when the cyanuric chloridewas replaced with cyanuric fluoride. Further, similar results wereobtained also when the compound of column 6 (and/or the compound(s) ofcolumn 5 and column 2 in case of having --SO₂ C₂ H₄ OH) was replacedwith the corresponding sulfuric ester derivative and the final step,namely conversion to a sulfuric ester, was omitted.

EXAMPLE 12

The same procedure as in Example 10 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 2-aminobenzenesulfonic acid and2-(β-hydroxyethylsulfonyl)ethylamine used in Example 10 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary and secondarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove. Further, similar results were obtained also when the compound ofcolumn 6 (and/or the compound(s) of column 5 and column 2 in case ofhaving --SO₂ C₂ H₄ OH) was replaced with the corresponding sulfuricester derivative and the final step, namely conversion to a sulfuricester, was omitted.

    TABLE 5      - 1 2 3 4 5 6 7      1     ##STR383##      ##STR384##      ##STR385##      H.sub.2 NC.sub.2 H.sub.4 OH H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4      OH Navyblue      2     ##STR386##      " " H.sub.2 NC.sub.2 H.sub.4 CO.sub.2 H H.sub.2 NC.sub.2 H.sub.4     OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      3     ##STR387##      " "      ##STR388##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      4     ##STR389##      ##STR390##      " NH.sub.3      ##STR391##      Navyblue      5 "     ##STR392##      ##STR393##      H.sub.2 NCH.sub.3 H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue      6     ##STR394##      ##STR395##      ##STR396##      ##STR397##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue      7     ##STR398##      ##STR399##      ##STR400##      NH.sub.3 " Navyblue      8     ##STR401##      ##STR402##      ##STR403##      H.sub.2      NCH.sub.3 " Navyblue      9     ##STR404##      " " H.sub.2 NC.sub.2 H.sub.4 OH H.sub.2 NC.sub.3 H.sub.6 SO.sub.2     C.sub.2 H.sub.4      OH Navyblue                    10      ##STR405##      ##STR406##      ##STR407##      H.sub.2 NC.sub.2 H.sub.5 H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4      Cl Navyblue           11 " " "      ##STR408##      " Navyblue     12 " " " HN(CH.sub.3).sub.2 " Navyblue     13 " " " H.sub.2 NC.sub.2 H.sub.4 CO.sub.2      H " Navyblue                                               14 " " " H.sub.2 NC.sub.2     H.sub.4 SO.sub.3      H " Navyblue                     15 " " "      ##STR409##      " Navyblue     16      ##STR410##      ##STR411##      ##STR412##      ##STR413##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                                                       17 " " "      ##STR414##      " Navyblue     18 " " "      ##STR415##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     19 " " "      ##STR416##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     20 " " "      ##STR417##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       21      ##STR418##      ##STR419##      ##STR420##      ##STR421##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       22 " " " " H.sub.2     NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue     23 " " "      ##STR422##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     24 " " "      ##STR423##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     25 " " "      ##STR424##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       26 " " " " H.sub.2     NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                              27      ##STR425##      ##STR426##      ##STR427##      ##STR428##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     28 " " "      ##STR429##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       29 " " "      ##STR430##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     30 " " " H.sub.2 NC.sub.2 H.sub.4 Cl H.sub.2 NC.sub.2 H.sub.4 SO.sub.2     C.sub.2 H.sub.4      OH Navyblue                    31 " " " NH.sub.3 " Navyblue     32 " " "      ##STR431##      " Navyblue     33 " " " H.sub.2      NCH.sub.3 " Navyblue                     34      ##STR432##      ##STR433##      ##STR434##      ##STR435##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       35 " " "      ##STR436##      " Navyblue     36 " " "      ##STR437##      " Navyblue     37 " " "      ##STR438##      " Navyblue     38 " " " H.sub.2 NC.sub.2 H.sub.4      OCH.sub.3 " Navyblue                                      39 " " "      ##STR439##      " Navyblue     40      ##STR440##      ##STR441##      ##STR442##      ##STR443##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     41 " " "      ##STR444##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       42 " "      ##STR445##      ##STR446##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH     Navyblue     43 " "      ##STR447##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      44      ##STR448##      ##STR449##      ##STR450##      ##STR451##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       45      ##STR452##      ##STR453##      ##STR454##      " " Navyblue     46      ##STR455##      "      ##STR456##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      47      ##STR457##      "      ##STR458##      " H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.2 SO.sub.2 C.sub.2 H.sub.4 OH N     avyblue     48      ##STR459##      ##STR460##      ##STR461##      ##STR462##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       49      ##STR463##      " "      ##STR464##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       50 " " "      ##STR465##      ##STR466##      Navyblue     51      ##STR467##      " "      ##STR468##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       52      ##STR469##      ##STR470##      ##STR471##      ##STR472##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       53      ##STR473##      " "      ##STR474##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue                                                       54      ##STR475##      "      ##STR476##      " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH Navyblue                                                                      55      ##STR477##      "      ##STR478##      " H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2     Navyblue     56      ##STR479##      ##STR480##      ##STR481##      ##STR482##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      OH Navyblue

EXAMPLE 13

The same procedure as in Example 5 was repeated, except that thecoupling reactions of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidwith the two diazo compounds were carried out in a reverse order, toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR483##

EXAMPLE 14

The same procedure as in Example 13 was repeated, using the samecompounds of columns 2-6 as used in Example 6, to obtain thecorresponding bisazo compounds. When used for dyeing, the compounds gavenavy blue-colored dyed products. Similar results were obtained when theabove-mentioned synthesis was repeated while changing the order ofprimary, secondary and tertiary condensation reactions with cyanuricchloride. Further, similar results were obtained also when cyanuricchloride was replaced with cyanuric fluoride.

EXAMPLE 15

The same procedure as in Example 13 was repeated, except that the2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, 4-aminobenzenesulfonic acid and3-(β-chloroethylsulfonyl)propylamine used in Example 13 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary, secondary and tertiarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove.

    TABLE 6      - 1 2 3 4 5 6 7      1     ##STR484##      ##STR485##      ##STR486##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 NH.sub.2 H.sub.2 NC.sub.3 H.sub.6     SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue      2     ##STR487##      " "      ##STR488##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Navyblue      3     ##STR489##      " " NH.sub.3 H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 Navyblue      4     ##STR490##      ##STR491##      ##STR492##      ##STR493##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue      5     ##STR494##      ##STR495##      ##STR496##      ##STR497##      H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Navyblue      6 " " "     ##STR498##      " Navyblue      7 " " "     ##STR499##      " Navyblue      8 " " "     ##STR500##      " Navyblue      9 " " "     ##STR501##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                             10 " " "      ##STR502##      " Navyblue      11      ##STR503##      ##STR504##      ##STR505##      ##STR506##      H.sub.2 NC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4      Cl Navyblue                             12 " " "      ##STR507##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Navyblue                                             13 " " "      ##STR508##      " Navyblue      14 " " "      ##STR509##      " Navyblue

EXAMPLE 16

In a usual manner, cyanuric chloride (3.69 parts) and2,4-diaminobenzenesulfonic acid (3.76 parts) were subjected to acondensation reaction with each other at pH 2-4 at a temperature of0°-10° C., and then with ethylamine (0.91 part) at pH 6-10 at atemperature of 20°-40° C. with stirring. After diazotizing thecondensate, the diazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH1-3.5 at a temperature of 0°-15° C., and further a diazotized product of2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts)was coupled therewith at pH 4-8 at a temperature of 0°-20° C. Finally,the thus obtained coupled product was condensed with1-aminobenzene-3-β-sulfatoethylsulfone (5.63 parts) at pH 2-5 at atemperature of 50°-80° C., and the thus condensed product was salted outto obtain a bisazo compound represented by the following formula in thefree acid form: ##STR510##

EXAMPLE 17

The synthesis of Example 16 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, ethylamine and1-aminobenzene-3-β-sulfatoethylsulfone were replaced with the compoundsshown in column 2, column 3, column 4, column 5 and column 6 of thefollowing table, respectively, to obtain the corresponding bisazocompounds. When used for dyeing, the bisazo compounds gave dyed productsof which hues were as shown in column 7 of the table. When theabove-mentioned synthesis was repeated while changing the order ofprimary and secondary condensation reactions with cyanuric chloride, theresults obtained were similar to those obtained above. Further, similarresults were obtained when the cyanuric chloride was replaced withcyanuric fluoride.

    TABLE 7      - 1 2 3 4 5 6 7      1     ##STR511##      ##STR512##      ##STR513##      NH.sub.3      ##STR514##      Navyblue      2 " " " CH.sub.3      NH.sub.2 " Navyblue      3 " " "     ##STR515##      " Navyblue      4     ##STR516##      " " HN(CH.sub.3).sub.2 " Navyblue      5     ##STR517##      " " H.sub.2 NC.sub.2      H.sub.5 " Navyblue      6     ##STR518##      ##STR519##      ##STR520##      NH.sub.3      ##STR521##      Navyblue      7     ##STR522##      ##STR523##      ##STR524##      ##STR525##      " Navyblue      8     ##STR526##      ##STR527##      ##STR528##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3      H     ##STR529##      Navyblue      9 " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3 H      ##STR530##      Navyblue     10 " " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3 H      ##STR531##      Navyblue     11      ##STR532##      ##STR533##      ##STR534##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3      H     ##STR535##      Navyblue     12 " " " H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2C.sub.2     H.sub.4 OSO.sub.3      H " Navyblue                      13      ##STR536##      " " H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3 H "     Navyblue     14 " " " H.sub.2 NC.sub.3 H.sub.6 SO.sub.2C.sub.2 H.sub.4 Cl " Navyblue     15 "      ##STR537##      " H.sub.2 NC.sub.2 H.sub.4 OC.sub.2 H.sub.4SO.sub.2      CHCH.sub.2     ##STR538##      Navyblue     16      ##STR539##      "      ##STR540##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3      H     ##STR541##      Navyblue     17      ##STR542##      ##STR543##      ##STR544##      H.sub.2 NC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 OSO.sub.3      H     ##STR545##      Navyblue

EXAMPLE 18

In a usual manner, cyanuric chloride (3.69 parts) and1-aminobenzene-4-β-sulfatoethylsulfone (5.63 parts) were subjected to acondensation reaction with each other at pH 2-5 at a temperature of5°-20° C. Then, an aqueous solution containing methylamine (0.63 part)was added and stirred at pH 6-10 at a temperature of 15°-40° C. to makeprogress a condensation reaction. Then, the product was furthercondensed with 2,4-diaminobenzenesulfonic acid (3.76 parts) at pH 2-5 ata temperature of 50°-80° C. After diazotizing the condensate, thediazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH0.5-3.5 at a temperature of 0°-15° C., and further a diazotized productof 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23parts) was coupled therewith at pH 4-8 at a temperature of 0°-20° C.Finally, the thus obtained coupled product was salted out with potassiumchloride to obtain a bisazo compound represented by the followingformula in the free acid form: ##STR546##

EXAMPLE 19

The synthesis of Example 18 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, methylamine and1-aminobenzene-4-β-sulfatoethylsulfone were replaced with the compoundsshown in column 2, column 3, column 4, column 5 and column 6 of thefollowing table, respectively, to obtain the corresponding bisazocompounds. When used for dyeing, the bisazo compounds gave dyed productsof which hues were as shown in column 7 of the table. When theabove-mentioned synthesis was repeated while changing the order ofprimary and secondary condensation reactions with cyanuric chloride, theresults obtained were similar to those obtained above. Further, similarresults were obtained when the cyanuric chloride was replaced withcyanuric fluoride.

    TABLE 8      - 1 2 3 4 5 6 7      1     ##STR547##      ##STR548##      ##STR549##      H.sub.2 NC.sub.2      H.sub.5     ##STR550##      Navyblue      2     ##STR551##      " " NH.sub.3      ##STR552##      Navyblue      3     ##STR553##      " " "      ##STR554##      Navyblue      4     ##STR555##      " " "      ##STR556##      Navyblue

EXAMPLE 20

The same procedure as in Example 16 was repeated, except that thecoupling reactions of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidwith the two diazo compounds were carried out in a reverse order, toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR557##

EXAMPLE 21

The same procedure as in Example 20 was repeated, using the samecompounds of columns 2-6 as used in Example 17, to obtain thecorresponding bisazo compounds. When used for dyeing, the compounds gavenavy-colored dyed products.

EXAMPLE 22

The same procedure as in Example 20 was repeated, except that the2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, ethylamine and1-aminobenzene-3-β-sulfatoethylsulfone used in Example 20 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary and secondarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove.

                                      TABLE 9                                     __________________________________________________________________________    1 2          3           4         5        6              7                  __________________________________________________________________________       ##STR558##                                                                               ##STR559##                                                                                ##STR560##                                                                             NH.sub.3                                                                                ##STR561##    Navy blue          2 "          "           "         "                                                                                       ##STR562##    Navy blue          3 "          "           "         H.sub.2 NCH.sub.3                                                                      "              Navy                                                                          blue               4                                                                                ##STR563##                                                                               ##STR564##                                                                                ##STR565##                                                                             HN(CH.sub.3).sub.2                                                                      ##STR566##    Navy blue          5                                                                                ##STR567##                                                                               ##STR568##                                                                                ##STR569##                                                                              ##STR570##                                                                             ##STR571##    Navy blue          6                                                                                ##STR572##                                                                               ##STR573##                                                                                ##STR574##                                                                              ##STR575##                                                                             ##STR576##    Navy blue          7 "          "           "         H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                                      "              Navy                                                  C.sub.2 H.sub.4 OSO.sub.3 H                                                                           blue               8 "          "           "         H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                             C.sub.2 H.sub.4 OSO.sub.3 H                                                             ##STR577##    Navy blue          9 "          "           "         H.sub.2 NC.sub.3 H.sub.6 SO.sub.2                                                      "              Navy                                                  C.sub.2 H.sub.4 OSO.sub.3 H                                                                           blue               10                                                                              "          "           "         H.sub.2 NC.sub.3 H.sub.6 SO.sub.2                                             C.sub.2 H.sub.4 OSO.sub.3 H                                                             ##STR578##    Navy blue          11                                                                               ##STR579##                                                                               ##STR580##                                                                                ##STR581##                                                                             H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                             C.sub.2 H.sub.4 OSO.sub.3 H                                                             ##STR582##    Navy blue          12                                                                              "          "                                                                                          ##STR583##                                                                             H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                             C.sub.2 H.sub.4 Cl                                                                      ##STR584##    Navy blue          13                                                                              "                                                                                         ##STR585##                                                                                ##STR586##                                                                             H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                             CHCH.sub.2                                                                             "              Navy blue          14                                                                               ##STR587##                                                                              "                                                                                          ##STR588##                                                                             H.sub.2 NC.sub.3 H.sub.6 SO.sub.2                                             C.sub.2 H.sub.4 OSO.sub.3 H                                                            "              Navy blue          15                                                                               ##STR589##                                                                               ##STR590##                                                                                ##STR591##                                                                             H.sub.2 NC.sub.2 H.sub.4 SO.sub.2                                             C.sub.2 H.sub.4 OSO.sub.3 H                                                             ##STR592##    Navy blue          16                                                                              "                                                                                         ##STR593## "         "                                                                                       ##STR594##    Navy blue          __________________________________________________________________________

EXAMPLE 23

The same procedure as in Example 18 was repeated, except that thecoupling reactions of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidwith the two diazo compounds were carried out in a reverse order, toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR595##

EXAMPLE 24

The same procedure as in Example 23 was repeated, using the samecompounds of columns 2-6 as mentioned in Example 19, to obtain thecorresponding bisazo compounds. When used for dyeing, the compounds gavenavy-colored dyed products.

EXAMPLE 25

The same procedure as in Example 23 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, methylamine and1-aminobenzene-4-β-sulfatoethylsulfone used in Example 23 were replacedwith the compounds of columns 2, 3, 4, 5 and 6 of the following table,respectively, to obtain the corresponding bisazo compounds. When usedfor dyeing, the bisazo compounds gave dyed products of which hues wereas shown in column 7 of the table. When the above-mentioned synthesiswas repeated while changing the order of primary and secondarycondensation reactions with cyanuric chloride, the results obtained weresimilar to those obtained above. When the cyanuric chloride was replacedwith cyanuric fluoride, the results were similar to those obtainedabove.

                                      TABLE 10                                    __________________________________________________________________________    1  2           3           4          5   6               7                   __________________________________________________________________________        ##STR596##                                                                                ##STR597##                                                                                ##STR598##                                                                              NH.sub.3                                                                           ##STR599##     Navy blue           2                                                                                 ##STR600## "           "          "   "               Navy blue           __________________________________________________________________________

EXAMPLE 26

In a usual manner, methanol (0.64 part) and cyanuric chloride (3.69parts) were subjected to a condensation reaction with each other andthen with 2,4-diaminobenzenesulfonic acid (3.76 parts). The condensatewas diazotized and then the diazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH1-3.5 at a temperature of 0°-15° C., and further a diazotized product of2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts)was coupled therewith at pH 3-8 at a temperature of 0°-30° C. Finally,the thus obtained coupled product was condensed with1-aminobenzene-3-β-sulfatoethylsulfone (5.63 parts) at pH 2-5 at atemperature of 50°-80° C., and the condensate was salted out withpotassium chloride to obtain a bisazo compound represented by thefollowing formula in the free acid form: ##STR601##

EXAMPLE 27

The synthesis of Example 26 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, methanol and1-aminobenzene-3-β-sulfatoethylsulfone used in Example 26 were replacedwith the compounds shown in column 2, column 3, column 4, column 5 andcolumn 6 of the following table, respectively, to obtain thecorresponding bisazo compounds. When used for dyeing, the bisazocompounds gave dyed products of which hues were as shown in column 7 ofthe table. Similar results were obtained when the cyanuric chloride wasreplaced with cyanuric fluoride.

                                      TABLE 11                                    __________________________________________________________________________    1  2          3           4        5       6              7                   __________________________________________________________________________        ##STR602##                                                                               ##STR603##                                                                                ##STR604##                                                                            CH.sub.3 OH                                                                            ##STR605##    Navy blue           2  "          "           "        C.sub.2 H.sub.5 OH                                                                     ##STR606##    Navy blue           3                                                                                 ##STR607##                                                                              "           "        CH.sub.3 OH                                                                           "              Navy blue           4  "          "           "        "                                                                                      ##STR608##    Navy blue           5                                                                                 ##STR609##                                                                               ##STR610##                                                                                ##STR611##                                                                            C.sub.2 H.sub.5 OH                                                                     ##STR612##    Navy blue           6                                                                                 ##STR613##                                                                              "           "        CH.sub.3 OH                                                                            ##STR614##    Navy blue           7                                                                                 ##STR615##                                                                              "           "        "                                                                                      ##STR616##    Navy blue           8                                                                                 ##STR617##                                                                               ##STR618## "        "                                                                                      ##STR619##    Navy blue           9                                                                                 ##STR620##                                                                               ##STR621##                                                                                ##STR622##                                                                            CH.sub.3 OH                                                                            ##STR623##    Navy blue           10                                                                                ##STR624##                                                                              "           "        "                                                                                      ##STR625##    Navy blue           11 "          "           "        "                                                                                      ##STR626##    Navy blue           12 "          "           "        "                                                                                      ##STR627##    Navy blue           13                                                                                ##STR628##                                                                               ##STR629##                                                                                ##STR630##                                                                            CH.sub.3 OH                                                                            ##STR631##    Navy blue           14 "          "           "        "                                                                                      ##STR632##    Navy blue           15                                                                                ##STR633##                                                                              "           "        "                                                                                      ##STR634##    Navy blue           16                                                                                ##STR635##                                                                               ##STR636##                                                                                ##STR637##                                                                            CH.sub.3 OH                                                                            ##STR638##    Navy blue           17 "                                                                                         ##STR639##                                                                                ##STR640##                                                                            "                                                                                      ##STR641##    Navy blue           18                                                                                ##STR642##                                                                               ##STR643##                                                                                ##STR644##                                                                            "       "              Navy blue           19 "          "           "        C.sub.2 H.sub.5 OH                                                                     ##STR645##    Navy blue           20                                                                                ##STR646##                                                                               ##STR647##                                                                                ##STR648##                                                                            CH.sub.3 CH.sub.2 OH                                                                  H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 CHCH.sub.2                                                                          Navy blue           21                                                                                ##STR649##                                                                              "                                                                                          ##STR650##                                                                            CH.sub.3 OH                                                                           H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue           22 "                                                                                         ##STR651## "        "       H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4 SO.sub.2                                                     CHCH.sub.2     Navy blue           23                                                                                ##STR652##                                                                               ##STR653## "        "       H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4 SO.sub.2                                                     C.sub.2 H.sub.4 Cl                                                                           Navy blue           __________________________________________________________________________

EXAMPLE 28

In a usual manner, methanol (0.64 part) and cyanuric chloride (3.69parts) were subjected to a condensation reaction with each other andthen with 1-ethylaminobenzene-4-β-sulfatoethylsulfone (6.19 parts) andfurther with 2,4-diaminobenzenesulfonic acid (3.76 parts) at pH 2-5 at atemperature of 50°-80° C. The condensate was diazotized in a usualmanner and then the diazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH1-3.5 at a temperature of 0°-15° C., and further a diazotized product of2-aminobenzene-5-β-sulfatoethylsulfone-1-sulfonic acid (7.23 parts) wascoupled therewith at pH 3-8 at a temperature of 0°-30° C. Finally, thethus obtained coupled product was salted out with potassium chloride toobtain a bisazo compound represented by the following formula in thefree acid form: ##STR654##

EXAMPLE 29

The synthesis of Example 28 was repeated, except that2-aminobenzene-5-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, methanol and1-ethylaminobenzene-4-β-sulfatoethylsulfone used in Example 28 werereplaced with the compounds shown in column 2, column 3, column 4,column 5 and column 6 of the following table, respectively, to obtainthe corresponding bisazo compounds. When used for dyeing, the bisazocompounds gave dyed products of which hues were as shown in column 7 ofthe table. Similar results were obtained when the cyanuric chloride wasreplaced with cyanuric fluoride.

                                      TABLE 12                                    __________________________________________________________________________    1 2          3          4          5         6              7                 __________________________________________________________________________       ##STR655##                                                                               ##STR656##                                                                               ##STR657##                                                                              CH.sub.3 OH                                                                              ##STR658##    Navy blue         2                                                                                ##STR659##                                                                              "          "          "         "              Navy blue         3 "          "                                                                                         ##STR660##                                                                              "         "              Navy blue         4                                                                                ##STR661##                                                                              "                                                                                         ##STR662##                                                                              CH.sub.3 CH(OH)CH.sub.3                                                                  ##STR663##    Navy blue         5                                                                                ##STR664##                                                                               ##STR665##                                                                               ##STR666##                                                                              CH.sub.3 (CH.sub.2).sub.3 OH                                                             ##STR667##    Navy blue         6                                                                                ##STR668##                                                                              "                                                                                         ##STR669##                                                                              CH.sub.3 OH                                                                              ##STR670##    Navy blue         7                                                                                ##STR671##                                                                               ##STR672##                                                                               ##STR673##                                                                              CH.sub.3 CH.sub.2 OH                                                                     ##STR674##    Navy blue         8                                                                                ##STR675##                                                                               ##STR676##                                                                               ##STR677##                                                                              CH.sub.3 OH                                                                              ##STR678##    Navy blue         9                                                                                ##STR679##                                                                              "          "          "                                                                                        ##STR680##    Navy blue         10                                                                              "          "          "          "                                                                                        ##STR681##    Navy blue         11                                                                              "          "          "          "                                                                                        ##STR682##    Navy blue         12                                                                               ##STR683##                                                                               ##STR684##                                                                               ##STR685##                                                                              CH.sub.3 OH                                                                              ##STR686##    Navy blue         13                                                                               ##STR687##                                                                              "          "          "         H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 CHCH.sub.2                                                                          Navy blue         14                                                                               ##STR688##                                                                              "          "          (CH.sub.3).sub.2 CHOH                                                                   H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         15                                                                              "          "          "          CH.sub.3 OH                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 CHCH.sub.2                                                                          Navy                                                                          blue              16                                                                               ##STR689##                                                                               ##STR690##                                                                               ##STR691##                                                                              "         H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 CHCH.sub.2                                                                          Navy blue         17                                                                               ##STR692##                                                                               ##STR693##                                                                               ##STR694##                                                                              CH.sub.3 OH                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                      OSO.sub.3 H    Navy blue         18                                                                              "          "          "          "         H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                      OSO.sub.3 H    Navy                                                                          blue              19                                                                               ##STR695##                                                                              "          "          "         H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                      OSO.sub.3 H    Navy blue         20                                                                              "          "          "          C.sub.2 H.sub.5 OH                                                                       ##STR696##    Navy blue         21                                                                               ##STR697##                                                                              "          "          CH.sub.3 OH                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                      OCOCH.sub.3    Navy blue         22                                                                               ##STR698##                                                                               ##STR699##                                                                               ##STR700##                                                                               ##STR701##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 CHCH.sub.2                                                                          Navy blue         23                                                                              "          "          "                                                                                         ##STR702##                                                                             "              Navy blue         24                                                                              "          "          "                                                                                         ##STR703##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         25                                                                               ##STR704##                                                                              "          "                                                                                         ##STR705##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         26                                                                               ##STR706##                                                                              "          "                                                                                         ##STR707##                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         27                                                                               ##STR708##                                                                               ##STR709##                                                                               ##STR710##                                                                               ##STR711##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         28                                                                              "          "          "                                                                                         ##STR712##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         29                                                                              "                                                                                         ##STR713##                                                                              "                                                                                         ##STR714##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         30                                                                               ##STR715##                                                                              "                                                                                         ##STR716##                                                                               ##STR717##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    CHH.sub.2      Navy blue         31                                                                              "          "          "          "         H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy                                                                          blue              __________________________________________________________________________

EXAMPLE 30

In a usual manner, methanol (0.64 part) and cyanuric chloride (3.69parts) were subjected to a condensation reaction with each other andthen with 2,4-diaminobenzenesulfonic acid (3.76 parts) and further withβ-(β-hydroxyethylsulfonyl)ethylamine (3.06 parts) at pH 6-10 at atemperature of 50°-90° C. The condensate was diazotized in a usualmanner and then the diazotized product was coupled with1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH1-3.5 at a temperature of 0°-15° C., and further a diazotized product of2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts)was coupled therewith at pH 3-8 at a temperature of 0°-30° C. Finally,the thus obtained coupled product was converted to a sulfuric ester in ausual manner and salted out to obtain a bisazo compound represented bythe following formula in the free acid form: ##STR718##

EXAMPLE 31

The synthesis of Example 30 was repeated, except that2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2,4-diaminobenzenesulfonic acid, methanol andβ-(β-hydroxyethylsulfonyl)ethylamine used in Example 30 were replacedwith the compounds shown in column 2, column 3, column 4, column 5 andcolumn 6 of the following table, respectively, to obtain thecorresponding bisazo compounds. When used for dyeing, the bisazocompounds gave dyed products of which hues were as shown in column 7 ofthe table. Similar results were obtained when the secondary and tertiarycondensation reactions with cyanuric chloride were carried out whilechanging the order of reaction. Further, similar results were obtainedalso when the cyanuric chloride was replaced with cyanuric fluoride.

                                      TABLE 13                                    __________________________________________________________________________    1 2          3          4          5         6              7                 __________________________________________________________________________       ##STR719##                                                                               ##STR720##                                                                               ##STR721##                                                                              CH.sub.3 OH                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         2                                                                                ##STR722##                                                                              "          "          "         "              Navy blue         3                                                                                ##STR723##                                                                              "          "          CH.sub.3 CH.sub.2 OH                                                                    "              Navy blue         4 "          "          "          CH.sub.3 OH                                                                              ##STR724##    Navy blue         5                                                                                ##STR725##                                                                               ##STR726##                                                                               ##STR727##                                                                              CH.sub.3 OH                                                                              ##STR728##    Navy blue         6                                                                                ##STR729##                                                                              "                                                                                         ##STR730##                                                                              "         H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4 SO.sub.2                                                     C.sub.2 H.sub.4 OH                                                                           Navy blue         7                                                                                ##STR731##                                                                              "          "          CH.sub.3 CH.sub.2 OH                                                                     ##STR732##    Navy blue         8                                                                                ##STR733##                                                                               ##STR734##                                                                               ##STR735##                                                                              CH.sub.3 CH.sub.2 OH                                                                     ##STR736##    Navy blue         9                                                                                ##STR737##                                                                               ##STR738##                                                                               ##STR739##                                                                              CH.sub.3 CH(OH)CH.sub.3                                                                 H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         10                                                                              "          "          "          CH.sub.3 OH                                                                             "              Navy                                                                          blue              11                                                                               ##STR740##                                                                              "          "          "         "              Navy blue         12                                                                              "          "          "                                                                                         ##STR741##                                                                             "              Navy blue         13                                                                               ##STR742##                                                                               ##STR743##                                                                               ##STR744##                                                                               ##STR745##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         14                                                                              "          "          "                                                                                         ##STR746##                                                                             "              Navy blue         15                                                                              "          "          "                                                                                         ##STR747##                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         16                                                                               ##STR748##                                                                              "          "          "         "              Navy blue         17                                                                               ##STR749##                                                                              "          "          "         H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         18                                                                               ##STR750##                                                                               ##STR751##                                                                               ##STR752##                                                                               ##STR753##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         19                                                                              "          "          "                                                                                         ##STR754##                                                                             "              Navy blue         20                                                                              "          "          "                                                                                         ##STR755##                                                                             "              Navy blue         21                                                                              "          "          "                                                                                         ##STR756##                                                                             "              Navy blue         22                                                                              "          "          "                                                                                         ##STR757##                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         23                                                                               ##STR758##                                                                               ##STR759##                                                                               ##STR760##                                                                               ##STR761##                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         24                                                                              "                                                                                         ##STR762##                                                                              "                                                                                         ##STR763##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         25                                                                               ##STR764##                                                                              "          "                                                                                         ##STR765##                                                                             H.sub.2 NC.sub.2 H.sub.4                                                      OC.sub.2 H.sub.4  SO.sub.2                                                    C.sub.2 H.sub.4 OH                                                                           Navy blue         26                                                                              "          "          "                                                                                         ##STR766##                                                                             H.sub.2 NC.sub.3 H.sub.6                                                      SO.sub.2 C.sub.2 H.sub.4                                                                     Navy blue         __________________________________________________________________________

EXAMPLE 32

Each bisazo compound obtained in Examples 1-31 (each 0.1, 0.3 and 0.6part) was dissolved in water (200 parts), and sodium sulfate (10 parts)and cotton (10 parts) were added thereto. The bath was heated to 60° C.,and then sodium carbonate (4 parts) was added thereto. Dyeing wascontinued for 1 hour at that temperature. Thereafter, the cotton takenout was washed with water, soaped, washed with water and then dried toobtain each dyed product of a navy blue color superior in fastnessproperties with a superior build-up property.

EXAMPLE 33

Using each bisazo compound described in Examples 1-31, each color pastehaving the following composition was prepared.

    ______________________________________                                        Bisazo compound       5 Parts                                                 Urea                  5 Parts                                                 Sodium alginate (5%) stock paste                                                                   50 Parts                                                 Hot water            25 Parts                                                 Sodium hydrogencarbonate                                                                            2 Parts                                                 Water                13 Parts                                                 ______________________________________                                    

Mercerized cotton broad cloth was printed with the color paste of theabove composition, pre-dried, steamed at 100° C. for 5 minutes, washedwith hot water, soaped, again washed with hot water, and then dried toobtain a product printed in a navy blue color superior in variousfastness properties.

What is claimed is:
 1. An amino compound represented by the followingformula (XIV) or a salt thereof: ##STR767## wherein R¹ is hydrogen orunsubstituted or substituted alkyl; B is a group represented by thefollowing formula (1) or (2): ##STR768## wherein the mark * means a bondlinking to the amino group, and R² is hydrogen, methyl or methoxy; andLis a triazinyl group represented by any one of the following formulas(IV) or (V): ##STR769## wherein R³ is hydrogen or unsubstituted orsubstituted alkyl; R⁸ is straight or branched alkyl unsubstituted orsubstituted with one or two substituents selected from alkoxy, sulfo,carboxy, alkyl carboxylate, hydroxy, cyano, sulfato, halogeno, phenyl,substituted phenyl, carbamoyl and sulfamoyl, or phenyl unsubstituted orsubstituted with one or two substituents selected from alkyl,substituted alkyl, alkoxy, substituted alkoxy, hydroxy, sulfo, cyano,carboxy, alkyl carboxylate, sulfamoyl, carbamoyl, substituted amino andhalogeno; R¹⁰ is hydrogen or straight or branched alkyl unsubstituted orsubstituted with one or two substituents selected from hydroxy,halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, alkyl carboxylate,carbamoyl, sulfamoyl, amino and dimethyl amino; R¹¹ is hydrogen,straight or branched alkyl unsubstituted or substituted with one or twosubstituents selected from hydroxy, halogeno, alkoxy, cyano, sulfo,sulfato, carboxy, alkyl carboxylate, carbamoyl, sulfamoyl, amino andsubstituted amino, or phenyl unsubstituted or substituted with one ortwo substituents selected from sulfo, alkyl, alkoxy, hydroxy, halogeno,cyano, carboxy, alkyl carboxylate, carbamoyl, sulfamoyl, amino,substituted amino, --SO₂ CH₂ CH₂ OH and SO₂ Z³, in which Z³ is --CH═CH₂or --CH₂ CH₂ Z' in which Z' is a group capable of being split by theaction of an alkali; or R¹⁰ and R¹¹ conjointly form a heterocyclic ringwhich may contain nitrogen, oxygen or sulfur as a ring atom; Z² is--CH═CH₂ or --CH₂ CH₂ Z' in which Z' is as defined above; and A is adivalent aliphatic group represented by the following formula (3), (4)or (5):

    --CH.sub.2 --W--                                           (3)

    --(CH.sub.2).sub.m --O--(CH.sub.2).sub.n --                (4) ##STR770## in which W is straight or branched chain C.sub.1 -C.sub.6 alkylene unsubstituted or substituted by chloro, bromo, fluoro, hydroxy, sulfato, cyano, C.sub.1 -C.sub.4 alkylcarbonyloxy, C.sub.1 -C.sub.5 alkoxycarbonyl, carboxy or carbamoyl; W.sup.1 and W.sup.2 independently of one another are each straight or branched chain C.sub.2 -C.sub.6 alkylene; R.sup.9 is hydrogen, unsubstituted lower alkyl or phenyl; and m and n independently of one another are each an integer of 2 to
 6.


2. A compound according to claim 1 or a salt thereof, wherein R¹ ishydrogen or methyl.
 3. A compound according to claim 1 or a saltthereof, wherein R³ is hydrogen, methyl or ethyl.
 4. A compoundaccording to claim 1 or a salt thereof, wherein B is a group representedby the following formula in the free acid form: ##STR771## wherein themark * is as defined in claim
 1. 5. A compound according to claim 1 or asalt thereof, wherein L is represented by the formula (III) in which R⁵is hydrogen, or L is represented by the formula (V) in which R¹⁰ ishydrogen.
 6. A compound according to claim 1 or a salt thereof, whereinL is represented by the formula (II) in which R⁷ is methyl or ethyl, orL is represented by the formula (IV) in which R⁸ is phenyl unsubstitutedor substituted by methyl, methoxy or sulfo.
 7. A compound according toclaim 1 or a salt thereof, wherein A is a group represented by thefollowing formula (6), (7) or (8):

    --CH.sub.2 CH.sub.2 --                                     (6)

    --CH.sub.2 CH.sub.2 CH.sub.2 --                            (7)

    --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --.                 (8)


8. A compound according to claim 1 or a salt thereof, wherein Z² and Z³independently of one another are each vinyl, β-sulfatoethyl orβ-chloroethyl.